Molluscicidal trifluoromethyl p-nitro diphenyl ethers

ABSTRACT

1-((XN,YM-PHENYL)-O-),2-CF3,4-(O2N-)BENZENE THE PRESENT INVENTION RELATES TO COMPOUNDS OF THE GENERAL FORMULA WHEREIN X IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HALOGEN ATOM, AN ALKYL GROUP HAVING 1 TO 4 CARBON ATOMS, THE GROU -OCH3, -SCH3, -NO2 AND -CF3, Y IS A MEMBER SELECTED FROM THE CLASS CONSISTING OF A HALOGEN ATOM AND AN ALKYL GROUP HAVING 1 TO 4 CARBON ATOMS, AND N AND M DENOTE INTEGERS FROM 0 TO 3, WHOSE SUM IS AT MOST 5, AS WELL AS TO MOLLUSCIDAL PREPARATION CONTAINING SUCH COMPOUNDS.

United States Patent 3,733,422 MOLLUSCICIDAL TRIFLUOROMETHYL p-NITRODIPHENYL ETHERS Otto Robr, Therwil, and Marcus von Orelli, Munchenstein,Switzerland, assignors to Ciba Limited, Basel, Switzerland No Drawing.Application Apr. 1, 1970, Ser. No. 24,851,

now Patent No. 3,647,888, which is a continuation-inpart of abandonedapplication Ser. No. 680,334, Nov. 3, 1967. Divided and this applicationNov. 19, 1971, Ser. No. 200,608

Int. Cl. A01n 9/24 U.S. Cl. 424-340 6 Claims ABSTRACT OF THE DISCLOSUREThe present invention relates to compounds of the general formula Thisis a division of application Ser. No. 24,851, filed Apr. 1, 1970, nowUS. Pat. No. 3,647,888, which is a continuation-in-part of applicationSer. No. 680,334, filed Nov. 3, 1967, now abandoned.

CROSS REFERENCE This is a continuation in part of application Ser. No.680,334 filed Nov. 3, 1967.

The present invention provides compounds of the general formula CFs Xu(1) wherein X represents a halogen atom, a lower alkyl group having 1 to4 carbon atoms or the groups OCH SCH, -N0 or CF Y represents a halgoenatom or a lower alkyl group having 1 to 4 carbon atoms and n or m denoteintegers from 0 to 3 whose sum is at most 5.

The present invention also provides mollusicicidal preparations, whichcomprise, as active ingredient, a compound of the above mentionedFormula I together with a suitable carrier.

The preparations may contain at least one of the following additives: asolvent, a diluent, a dispersing agent, a wetting agent and an adhesive,as well as other pesticides.

Those preparations which contain, as the active substance, the compoundof formula are especially effective in combating water snails and have asurprisingly low toxicity to fish.

The invention further provides the following process for the manufactureof the new compounds of Formulae I and II.

The new compounds of General Formula I are manufactured by reacting2-chloro-5-nitrobenzotrifluoride with a compound of general formulawherein X, Y, n and m have the significance given above for the case ofthe General Formula I, with elimination of hydrogen chloride and in thepresence of an acid acceptor, preferably an alkali hydroxide, optionallyin a polar solvent, at a temperature within the range' of from 0 to 200C.

The compounds of General Formula I all exhibit an excellent effectagainst molluscs and their eggs.

The preparations according to the invention may be used in the mostdiverse application forms. Possible substance for the manufacture ofdirectly sprayable solutions of the compounds of General Formula I are,for example, mineral oil fractions of high to medium boiling range,preferably having a boiling range above C., for example, diesel oil orkerosene, coal tar oils and oils of vegetable or animal origin, as wellas hydrocarbons, for example, alkylated naphthalenes andtetrahydronaphthalene, optionally with the use of xylene mixtures,cyclohexanols, ketones, and furthermore chlorinated hydrocarbons, forexample, trichloroethane and tetrachloroethane, trichloroethylene ortrichlorobenzenes and tetrachlorobenzenes.

Aqueous application forms are, for example, prepared from emulsionconcentrates, pastes or Wettable spraying powders by adding water.Possible emulsifiers or dispersing agents are, for example, non-ionicproducts, for example, condensation products of aliphatic alcohols,amines or carboxylic acids having a long chain hydrocarbon residuecontaining about 10 to 12 carbon atoms, with ethylene oxide, for examplethe condensation product of octadecyl alcohol and 25 to 30 mols ofethylene oxide or that of soya fatty acid and 30 mols of ethylene oxideor that of commercial oleylamine and 15 mols of ethylene oxide or thatof dodecylmercaptan and 12 mols of ethylene oxide. Amongst the anionicemulsifiers which may be used, there may be mentioned: the sodium saltof dodecyl alcohol sulphuric acid ester, the sodium salt ofdodecylbenzenesulphonic acid, the potassium or triethanolamine salt ofoleic acid or of abietic acid or of mixtures of these acids or thesodium saltipf a petroleum sulphonic acid. Cationic dispersing agentsthat may be used are quaternary ammonium compounds, for example, cetylpyridinium bromide, or dihydroxyethylbenzyl dodecyl ammonium chloride.

In order to prepare dusting and scattering agents, talc, kaolin,bentonite, calcium carbonates, calcium phosphate, and also charcoal,cork powder, wood flour and other materials of vegetable origin may beused as solid carriers. It is also very advantageous to manufacture thepreparations in a granulated form. The various application forms may beprovided with the addition of substances which improve the distribution,adhesion, rain resistance or penetrating power, in the usual manner. Assuch substances there may be mentioned fatty acids, resins, glue, caseinor alginates.

The preparations according to the invention may be used by themselves ortogether with conventional pesticides, such as insecticides, acaricides,nematocides, bac tericides, fungicides and/ or herbicides.

In the following examples, which illustrate the invention, the partsdenote parts by weight unless otherwise stated, and the percentagesdenote percentage by weight.

EXAMPLE 1 32.6 g. of 3,4-dichlorophenol are dissolved in 50 ml. ofdimethylformamide in a flask provided with a stirrer. This solution ismixed with 11.2 g. of potassium hydroxide dissolved in 10 ml. of Waterand 49.6 g. of 2- chloro-S-nitro-benzotrifluoride are thereafter addeddrop by drop. The reaction mixture is heated to reflux temperatures(sic) for 2 hours and is then subjected to a steam distillation. Theoily residue is extracted with ether. After distilling oif the solvent,crystals having a melting point of 9799 C. are obtained.

The following compounds were also manufactured in a similar manner.

2. R Q Bolling point (0.02): 113-123.

3. Melting point: 7072.

R Cl

4- Melting point: 7377.

5. Meltin point: 6840.

CPI;

0- Boiling point(0.03): 122128.

7. (3H3 Melting point: 14l-147.

8. Melting point: 49-52.

R=- CH;

9- Melting point: 7072.

R= 0 GHQ 10. Melting point: 54-55.

R Br

11- R Q Boiling point (0.03): 131134.

12. (2H Melting point: 5860.

13. Cl Boiling point (0.02): 152-158.

Melting point: 7273.

15...; Q Boiling point (0.02): 123-129.

16.... CH; Boiling point (0.3): 174-178.

R S C H:

17. CH3 Melting point: -137.

18- (I) F; Melting point: 60-62.

19. ('3 F; Melting point: 76-78.

20- R I Melting point: 97101.

21. NO 9 Melting point: 123-129.

22. R s CH3 Boiling point (0.05): -170.

23-... CH; Boiling point (0.001): 132135.

EXAMPLE 2 10 parts of one of the compounds according to Example 1 are ineach case mixed with 15 parts of isooctylphenylpolyethoxy-ethanol anddiluted to 100 cm. with acetone.

A clear solution was obtained, which was used as a spraying materialconcentrate and which could be emulsified by being poured into Water.

EXAMPLE 3 Compound according to Concentration Example 1: in p.p.m. No.0.2-0.4

No. 4 3 No. 12 3 A similar good effect was also shown by the remainingcompounds described in Example 1.

We claim:

1. A molluscicidal preparation which comprises a molluscicidal amount ofa compound of the formula Fa n wherein X is a member selected from thegroup consisting of a halogen atom, an alkyl group having 1 to 4 carbonatoms, the group -OCH --SCH N0, and -CF;,, Y is a member selected fromthe class consisting of a halogen atom and an alkyl group having 1 to 4carbon atoms, and n and m denote integers from to 3, whose sum is atmost '5 in admixture with a pesticidally suitable carrier.

2. The preparation of claim 1 wherein the compoundis 3. The preparationof claim 1 wherein the compound is CF; H3 4. A method for kilingmollusos which comprises applying thereto a molluscicidally effectiveamount of a compound of the formula G F! I:

wherein X is a member selected from the group consisting of a halogenatom, an alkyl gorup having 1 to 4 carbon atoms, the group -OCH -SOH -NOand 6. The method of claim 4 wherein the compound is F3 H8 ReferencesCited UNITED STATES PATENTS 3,420,892 1/1969 Martin et a1. 2606122,464,877 3/1949 Markarian et al. 260-612 3,506,720 4/1970 Model et a1.260-612 3,558,720 1/1971 Schmidt et a1. 260-612 ALBERT T. MYERS, PrimaryExaminer N. A. DREZIN, Assistant Examiner

